CN108069897A - A kind of method using carbon dioxide synthesis niacin - Google Patents
A kind of method using carbon dioxide synthesis niacin Download PDFInfo
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- CN108069897A CN108069897A CN201610992599.0A CN201610992599A CN108069897A CN 108069897 A CN108069897 A CN 108069897A CN 201610992599 A CN201610992599 A CN 201610992599A CN 108069897 A CN108069897 A CN 108069897A
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- niacin
- carbon dioxide
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 54
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229960003512 nicotinic acid Drugs 0.000 title claims abstract description 47
- 235000001968 nicotinic acid Nutrition 0.000 title claims abstract description 47
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 27
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 21
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000019441 ethanol Nutrition 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000005763 3-bromopyridine Chemical group 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 238000013329 compounding Methods 0.000 claims abstract 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 17
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000003317 industrial substance Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000001914 filtration Methods 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 238000010583 slow cooling Methods 0.000 description 8
- 238000005292 vacuum distillation Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 235000016804 zinc Nutrition 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- MFEIKQPHQINPRI-UHFFFAOYSA-N 3-Ethylpyridine Chemical compound CCC1=CC=CN=C1 MFEIKQPHQINPRI-UHFFFAOYSA-N 0.000 description 2
- -1 Nicotinicum Acidum Chemical compound 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- YAPQBXQYLJRXSA-UHFFFAOYSA-N theobromine Chemical compound CN1C(=O)NC(=O)C2=C1N=CN2C YAPQBXQYLJRXSA-UHFFFAOYSA-N 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- NYPYPOZNGOXYSU-UHFFFAOYSA-N 3-bromopyridine Chemical compound BrC1=CC=CN=C1 NYPYPOZNGOXYSU-UHFFFAOYSA-N 0.000 description 1
- 150000005760 3-chloropyridine Chemical class 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000005515 coenzyme Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical class [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229960004559 theobromine Drugs 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The present invention discloses a kind of new method using carbon dioxide synthesis niacin, belongs to organic chemicals synthesis field, by 3 haloperidids, carbon dioxide is raw material, and ethyl alcohol makees solvent, and niacin is directly prepared under catalyst action；The catalyst is characterized in that catalyst activity component is made of palladium and diethyl zinc compounding, and catalyst amount is 3 bromopyridines：Catalyst=20：1~2 weight ratio, 100~250 DEG C of reaction temperature, 1~10 MPa of reaction pressure, 1~5 h of reaction time；The present invention is by carbon dioxide directly as industrial chemicals synthesis of chemicals, this is main, is also the more valuable mode using carbon dioxide, and the yield of purpose product and selectivity are higher, advantageously reduce the production cost of niacin, have good industrial application value.
Description
Technical field
The present invention relates to a kind of synthesis of niacin, and in particular to by 3- haloperidids, carbon dioxide is raw material, ethyl alcohol is molten
Agent, the method for preparing niacin in the presence of a catalyst belong to organic chemicals synthesis technical field.
Background technology
Niacin, i.e. Nicotinicum Acidum, also known as Buddhist nun's theobromine, abbreviation VB3, molecular formula is：C6H5NO2, structural formula is：, molecular weight 123.11, white or faint yellow acicular crystal or powder, odorless or micro- smelly, taste is slightly sour.Density
1.4738 g/cm3,234 ~ 238 DEG C of fusing point.Stable in the air and non-hygroscopic, aqueous solution shows acid.It is slightly molten in water,
It is readily soluble in boiling water, boiling ethyl alcohol, sodium hydroxide solution.Niacin combines to form coenzyme with protein in vivo, participates in body oxidation
Reduction, one of nutritional ingredient necessary to be animal body.Niacin is that structure is most simple in all vitamins, and physicochemical property is most stable
A kind of vitamin, it is not easy to by acid, alkali, metal ion, heat, light, oxidant and processing storage etc. factors destroy.Niacin is one
The important organic synthesis raw material of kind, the industries such as application field covering medicine, food, feed addictive and auxiliary chemicals.
There are many production method of niacin.The synthetic method of niacin mainly includes at present：Reagent oxidation method (nitric acid, permanganic acid
Potassium etc.), ammonia oxidation, liquid phase oxidation, air direct oxidation method, electrolytic oxidation, biological oxidation process and pyridine hydroxylating method
Deng.But compare from economy and technique, these methods all have certain deficiency：Reagent direct oxidation method is although easy to operate,
Oxidant source is extensive, but generally requires higher temperature or pressure, and product purity is low, and color and luster is not good enough, and three-waste pollution is serious, at present
Developed country oneself eliminated this method.Ammonia oxidation its it is apparent the shortcomings that be from raw material alkyl pyridine be made product need at least two steps
Independent chemical reaction, increases equipment investment.The key problem in technology of vapour phase oxidation process one-step synthesis niacin is to screen a kind of choosing
Selecting property is good, the high-quality catalyst of high conversion rate, etc..In recent years, using carbon dioxide as carbon oxygen resource chemical utilization increasingly by
To attention, in view of above-mentioned route there are the shortcomings that and utility value of the carbon dioxide as important carbon oxygen resource, it is necessary to develop
One efficient and environmental-friendly synthetic route realizes carbon dioxide low cost cleaning synthesis niacin.
The content of the invention
The technical problems to be solved by the invention be for the above-mentioned prior art present situation and a kind of simple for process, operation is provided
It is convenient, waste less, at low cost, high conversion rate and using carbon dioxide and 3- haloperidids as raw material, utilize catalyst synthesis cigarette
The method of acid.
In order to achieve the above object, the present invention adopts the following technical scheme that：
A kind of new method using carbon dioxide synthesis niacin, it is characterised in that：This method is with 3- haloperidids, carbon dioxide
Raw material, ethyl alcohol are solvent, are reacted under catalyst action, and 3- haloperidids are ethyl alcohol with ethyl alcohol molar ratio：The halogenated pyrroles of 3-
Pyridine=5~30：1,100~250 DEG C of reaction temperature, 1~10 Mpa of reaction pressure, 1~5 h of reaction time catalyze and synthesize niacin；
The catalyst is palladium and diethyl zinc compound；
The catalyst amount is 3- haloperidids：Catalyst=10：1 weight ratio；
Palladium and diethyl zinc ratio are in the compound catalyst:Palladium：Diethyl zinc=5：1 weight ratio；
The 3- haloperidids are ethyl alcohol with ethyl alcohol molar ratio：3- haloperidid=20：1；
The 3- haloperidids are 3- bromopyridines；
The catalyst is palladium and diethyl zinc compound；
Palladium and diethyl zinc ratio are in the compound catalyst:Palladium：Diethyl zinc=5：1 weight ratio；
The reaction temperature is 200 DEG C, and reaction pressure is 5 MPa, and the reaction time is 3 h；
Compared with prior art, the advantage of the invention is that main purpose product once through yield is up to 87%, Main By product is
Pyridine and 3-ethylpyridine, yield can be less than 5%, while overcome the former technically deficiency big to equipment corrosion, not only technique
Simply, and operation is more convenient, and waste is less, and cost is lower, and conversion ratio is also relatively high, therefore the present invention is with very big
The prospect of marketing.
Specific embodiment
In order to be better described the technical solution of this programme, typical but non-limiting embodiment is as follows in the present invention：
Embodiment 1：
In 150 mL stainless steel autoclaves, add in 3- bromopyridines 3.16 g, 36.86 g of ethyl alcohol, add in 0.26 g palladiums and
0.06 g diethyl zincs are catalyst compounded.After closed reactor, the carbon dioxide of 5 Mpa purity 99.9%, magneton rotating speed are filled with
Under the conditions of 180 r/min, temperature controller control temperature program(me) is warming up to 200 DEG C, reacts 3 h, is cooled to room temperature, gas reactor leads to
Over-pressed force control valve slowly excludes reactor, is absorbed with alcohol solvent, treat gas reactor release finish, open kettle collect reaction solution and
Absorbing liquid is placed in cucurbit and is evaporated under reduced pressure in 105 DEG C or so, until close to being evaporated, distillates part and is condensed back to
It receives, in case recycling；Pyridine is more completely removed through vacuum distillation, but inevitably also by-product etc. is other miscellaneous
The presence of matter, the solid matter that vacuum distillation is obtained are dissolved with 10% sodium hydroxide solution, it is miscellaneous to be filtered to remove insoluble matter etc.
Obtained filtrate is heated and concentrated, while hot with hydrochloric acid tune pH value to 3.5 by matter；The solution slow cooling for mixing up pH value is cooled down, together
Shi Jinhang is slowly stirred, 30 r/min of mixing speed, when temperature is down to 20 DEG C, crystal is precipitated, crude product niacin is obtained by filtration；It will
Crude product niacin presses 1 with water：4 mass ratio dissolves by heating, and temperature is not less than 60 DEG C, and slow cooling cooling is carried out at the same time and slowly stirs
It mixes, 30 r/min of mixing speed, temperature is down to 15 DEG C, and crystal is precipitated, niacin finished product is obtained by filtration；The niacin that will be obtained by filtration
At 100 DEG C, when drying 2 is small, finished product niacin, yield are obtained：86.3%；
Embodiment 2：
In 150 mL stainless steel autoclaves, add in 3- bromopyridines 3.16 g, 36.86 g of ethyl alcohol, add in 0.26 g nickel acetates and
0.06 g diethyl zincs are catalyst compounded.After closed reactor, the carbon dioxide of 5 Mpa purity 99.9%, magneton rotating speed are filled with
Under the conditions of 180 r/min, temperature controller control temperature program(me) is warming up to 200 DEG C, reacts 3 h, is cooled to room temperature, gas reactor leads to
Over-pressed force control valve slowly excludes reactor, is absorbed with alcohol solvent, treat gas reactor release finish, open kettle collect reaction solution and
Absorbing liquid is placed in cucurbit and is evaporated under reduced pressure in 105 DEG C or so, until close to being evaporated, distillates part and is condensed back to
It receives, in case recycling；Pyridine is more completely removed through vacuum distillation, but inevitably also by-product etc. is other miscellaneous
The presence of matter, the solid matter that vacuum distillation is obtained are dissolved with 10% sodium hydroxide solution, it is miscellaneous to be filtered to remove insoluble matter etc.
Obtained filtrate is heated and concentrated, while hot with hydrochloric acid tune pH value to 3.5 by matter；The solution slow cooling for mixing up pH value is cooled down, together
Shi Jinhang is slowly stirred, 30 r/min of mixing speed, when temperature is down to 20 DEG C, crystal is precipitated, crude product niacin is obtained by filtration；It will
Crude product niacin presses 1 with water：4 mass ratio dissolves by heating, and temperature is not less than 60 DEG C, and slow cooling cooling is carried out at the same time and slowly stirs
It mixes, 30 r/min of mixing speed, temperature is down to 15 DEG C, and crystal is precipitated, niacin finished product is obtained by filtration；The niacin that will be obtained by filtration
At 100 DEG C, when drying 2 is small, finished product niacin, yield are obtained：50.5%；
Embodiment 3：
In 150 mL stainless steel autoclaves, add in 3- bromopyridine 6.32g, 36.86 g of ethyl alcohol, add in 0.26 g palladiums and
0.06 g diethyl zincs are catalyst compounded.After closed reactor, the carbon dioxide of 5 Mpa purity 99.9%, magneton rotating speed are filled with
Under the conditions of 180 r/min, temperature controller control temperature program(me) is warming up to 200 DEG C, reacts 3 h, is cooled to room temperature, gas reactor leads to
Over-pressed force control valve slowly excludes reactor, is absorbed with alcohol solvent, treat gas reactor release finish, open kettle collect reaction solution and
Absorbing liquid is placed in cucurbit and is evaporated under reduced pressure in 105 DEG C or so, until close to being evaporated, distillates part and is condensed back to
It receives, in case recycling；Pyridine is more completely removed through vacuum distillation, but inevitably also by-product etc. is other miscellaneous
The presence of matter, the solid matter that vacuum distillation is obtained are dissolved with 10% sodium hydroxide solution, it is miscellaneous to be filtered to remove insoluble matter etc.
Obtained filtrate is heated and concentrated, while hot with hydrochloric acid tune pH value to 3.5 by matter；The solution slow cooling for mixing up pH value is cooled down, together
Shi Jinhang is slowly stirred, 30 r/min of mixing speed, when temperature is down to 20 DEG C, crystal is precipitated, crude product niacin is obtained by filtration；It will
Crude product niacin presses 1 with water：4 mass ratio dissolves by heating, and temperature is not less than 60 DEG C, and slow cooling cooling is carried out at the same time and slowly stirs
It mixes, 30 r/min of mixing speed, temperature is down to 15 DEG C, and crystal is precipitated, niacin finished product is obtained by filtration；The niacin that will be obtained by filtration
At 100 DEG C, when drying 2 is small, finished product niacin, yield are obtained：77.6%；
Embodiment 4：
In 150 mL stainless steel autoclaves, add in 3- chloropyridines 2.27 g, 36.86 g of ethyl alcohol, add in 0.26 g palladiums and
0.06 g diethyl zincs are catalyst compounded.After closed reactor, the carbon dioxide of 5 Mpa purity 99.9%, magneton rotating speed are filled with
Under the conditions of 180 r/min, temperature controller control temperature program(me) is warming up to 200 DEG C, reacts 3 h, is cooled to room temperature, gas reactor leads to
Over-pressed force control valve slowly excludes reactor, is absorbed with alcohol solvent, treat gas reactor release finish, open kettle collect reaction solution and
Absorbing liquid is placed in cucurbit and is evaporated under reduced pressure in 105 DEG C or so, until close to being evaporated, distillates part and is condensed back to
It receives, in case recycling；Pyridine is more completely removed through vacuum distillation, but inevitably also by-product etc. is other miscellaneous
The presence of matter, the solid matter that vacuum distillation is obtained are dissolved with 10% sodium hydroxide solution, it is miscellaneous to be filtered to remove insoluble matter etc.
Obtained filtrate is heated and concentrated, while hot with hydrochloric acid tune pH value to 3.5 by matter；The solution slow cooling for mixing up pH value is cooled down, together
Shi Jinhang is slowly stirred, 30 r/min of mixing speed, when temperature is down to 20 DEG C, crystal is precipitated, crude product niacin is obtained by filtration；It will
Crude product niacin presses 1 with water：4 mass ratio dissolves by heating, and temperature is not less than 60 DEG C, and slow cooling cooling is carried out at the same time and slowly stirs
It mixes, 30 r/min of mixing speed, temperature is down to 15 DEG C, and crystal is precipitated, niacin finished product is obtained by filtration；The niacin that will be obtained by filtration
At 100 DEG C, when drying 2 is small, finished product niacin, yield are obtained：11.6%；
The above is only some embodiments of the present invention, but the invention is not limited in above-mentioned method detaileds.Affiliated technology
The personnel in field pass through the methods of equivalence replacement or addition auxiliary element pairs in the technical scope of present disclosure, to the present invention
Any improvement that the present invention carries out should all be covered within the scope of the present invention.
Claims (9)
- A kind of 1. method using carbon dioxide synthesis niacin, it is characterised in that：This method is with 3- haloperidids, carbon dioxide Raw material, ethyl alcohol are solvent, are reacted under catalyst action, and 3- haloperidids are ethyl alcohol with ethyl alcohol molar ratio：The halogenated pyrroles of 3- Pyridine=5~30：1,100~250 DEG C of reaction temperature, 1~10 MPa of reaction pressure, 1~5 h of reaction time catalyze and synthesize niacin；Specific synthetic route is as follows：。
- 2. a kind of new method using carbon dioxide synthesis niacin as described in claim 1, it is characterised in that：The 3- halogen It is ethyl alcohol for pyridine and ethyl alcohol molar ratio：3- haloperidid=5~30：1, preferred alcohol：3- haloperidid=20：1.
- 3. a kind of new method using carbon dioxide synthesis niacin as described in claim 1, it is characterised in that：The 3- Haloperidid is 3- bromopyridines.
- 4. a kind of new method using carbon dioxide synthesis niacin as described in claim 1, it is characterised in that：The catalysis Agent is palladium and diethyl zinc compound.
- 5. a kind of new method using carbon dioxide synthesis niacin as described in claim 1, it is characterised in that：The compounding Palladium and diethyl zinc ratio are in object catalyst:Palladium：Diethyl zinc=1~10:1 weight ratio, preferably palladium：Two Zinc ethyl=5：1.
- 6. a kind of new method using carbon dioxide synthesis niacin as described in claim 1, it is characterised in that：The catalysis Agent dosage is that catalyst amount is 3- haloperidids：Catalyst=20：1~5 weight ratio, preferably 3- haloperidids：Catalyst=10： 1。
- 7. a kind of new method using carbon dioxide synthesis niacin as described in claim 1, it is characterised in that：The reaction Temperature is 100~250 DEG C, preferably 200 DEG C.
- 8. a kind of new method using carbon dioxide synthesis niacin as described in claim 1, it is characterised in that：The reaction Pressure is 1~10 MPa, preferably 5 Mpa.
- 9. a kind of new method using carbon dioxide synthesis niacin as described in claim 1, it is characterised in that：The reaction Time is 1~5 h, preferably 3 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610992599.0A CN108069897B (en) | 2016-11-11 | 2016-11-11 | Method for synthesizing nicotinic acid by using carbon dioxide |
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| CN201610992599.0A CN108069897B (en) | 2016-11-11 | 2016-11-11 | Method for synthesizing nicotinic acid by using carbon dioxide |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2311788A1 (en) * | 2009-10-14 | 2011-04-20 | Intitut Català d'Investigació Química (ICIQ) | Process for the carboxylation of aryl halides with palladium catalysts |
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2016
- 2016-11-11 CN CN201610992599.0A patent/CN108069897B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2311788A1 (en) * | 2009-10-14 | 2011-04-20 | Intitut Català d'Investigació Química (ICIQ) | Process for the carboxylation of aryl halides with palladium catalysts |
Non-Patent Citations (2)
| Title |
|---|
| ARKAITZ CORREA ET AL.: "Palladium-Catalyzed Direct Carboxylation of Aryl Bromides with Carbon Dioxide", 《J.AM.CHEM.SOC.》 * |
| SIGNE KORSAGER ET AL.: "Effective Palladium-Catalyzed Hydroxycarbonylation of Aryl Halides with Substoichiometric Carbon Monoxide", 《J.AM.CHEM.SOC.》 * |
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